Dyeing of artificial fibers



nite States 3,043,646 DYEING F ARTIFICIAL FIBERS Paul Buecheler, Reinach, Switzerland, assignor to Sandoz Ltd., Basel, Switzerland No Drawing. Filed Mar. 16, 1959, Ser. No. 799,442

Claims priority, application Switzerland Mar. 19, 1958 6 Claims.- (Cl. 840) It has been found that the anthraquinone dyestuffs of the formula atent 0 "ice aryl radical which may be further substituted, used alone or in mixtures with each other are eminently suitable for the dyeing of cellulose ester, synthetic polyamide and polyester fibers from aqueous suspension.

In many cases the mixtures of two or more dyestuffs of the Formula I show better building-up properties'than the dye-stuffs used alone.

The dyeing operation is conducted advantageously in presence of wetting, dispersing or emulsifying agents such as Marseilles soap, fatty alcohol sulfonates or sulfates, e.g. sodium lauryl sulfate, or the condensation products of fatty acids, e.g. oleic acid, with the alkali metal salts of aminoand methyl-amino-ethane-sulfonic acid, highly sulfonated castor oil, etc.

The dyeing temperatures and times depend upon the material to be dyed and are correlated with each other. Secondary cellulose acetate can be dyed at temperatures between 75 and 90 0, preferably at 80-85 C., for 45 minutes to 1 /2 hours, preferably for 1 hour. But it is also possible to work at 95 l00 C. e'.g. in the case of blended fabrics containing viscose and acetate, and even at about 120 C. under pressure, with a corresponding reduction of the dyeing time.

Cellulose triacetate and the synthetic polyamide fibers and dyed at 90-l00 C. for 45 minutes to l /zhours, preferably for 1 hour at the boil, or at temperatures between 105 and 120 C. under pressure, whereby the dyeing time can be shortened.

Polyester fibers, when dyed for about 1 hour at 95- 100 C., require thepresence of a carrier: 2-hydroxyl.l-diphenyl, the methyl ester of 2-hydroxybenzene-lcarboxylic acid, benzoic acid or an emulsion of chlorinated benzene, whereas at temperatures higher than 100 0., eg between 110 and 130 C. the addition of a carrier is superfluous.

In any event when the dyeing temperature exceeds 100' C. and in the case of secondary cellulose acetate already when the dyeing temperature amounts to 95 100 C., the dyebath must be maintained neutral in order to prevent saponification of the fibers.

at least one O-X-group in which X' 3,043,646 Patented July 10, 1!)62 To enhance the degree of dispersion, the dry 'dyestulfs may be preliminarily ground with a suitable Wetting or dispersing agent, such as sodium dinaphthylmethanedisulfonate, sodium ligninsulfonate or the dried residue of sulfite waste liquor. The dyestuifsmay also be intimately mixed in the form of an aqueous paste with one of the atorecited wetting or dispersing agents and, if desired, converted into the form of a dyestuff powder by suitable drying.

The dyeings obtained with these dyestuffs on secondary cellulose acetate possess excellent lightfastness and good fastness to washing, perspiration and gas fumes. On cellulose triacetate and polyester fibers they give dyeings of very good fastness to light, heat setting andpleating,

and good fastness to washing and perspiration. The dyestuffs reserve wool, cotton and viscose rayon.

The dyeings on synthetic polyamide fibers are fast to light, washing and perspiration.

In Formula I R preferably represents a mono-, dior trihydroxyphenyl radical, a monohydroxy, monomethoxyor monoethoxynaphthyl radical, a monoor dimethoxyor .-ethoxy-phenyl radical or a monohydroxymonomethoxyor -monoe thoxy-pheny1 radical.

Of the anthraquinone dyestuffs of Formula 1, those of the formula HO NH:

I The dyestuif gives a good reserve of wool. To improve .NH: 2% 01H (II) wherein R stands for a hydroxyphenyl, hydroxynaphthyl, methoxyphenyl or dihydroxyphenyl radical, are already known. They are obtained e.g. by (1) addition of phenol at the boric acid ester of 1.5-dihydroxy-4.8-diaminoanthraquinone-Z.6-disulfonic acid in concentrated sulfuric acid solution (GP 445,268), (2) boiling the addition product in acid aqueous solution or heating it in alkaline solution at 20-60 C. to split off one sulfonic acid group (GP 446,563), (3) reductive splitting off from the latter of the remaining sulfonic acid group (GP 456,235). I

The anthraquinone dyestuffs used in the present process are produced in an analogous manner.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

Example 1 A dyebath is prepared'with 1 part of the dyestufi 1.5- dihydroxy 4.8 -di-amino 2 (4-hydroxy)-phenylanthraquinone dispersed with Turkey red oil, 6 parts of a sulfonated fatty alcohol, and 3000 parts of water. parts of cellulose triacetate are entered in the bath at room temperature and the temperature is raised to 100 in 1 hour and maintained at 100 for a further hour. After this time the dyeing process is completed. The goods are removed, rinsed and dried. They are dyed a blue shade of good fastness to washing, gas fumes, heat setting and pleating, and very good light fastness.

Example 2v 1 part of 1.5-dihydroxy-4.8-diamino-2-(4'-methoxy)- phenylanthraquinone, 1 part of the sodium salt of di-.

naphthylmethanedisulfouic acid and 8 parts of water are ground together until a fine dispersion is formed. It is run into a dyebath consisting of 3000 parts of-water and 6 parts of Marseilles soap. 100 parts of a cellulose ace--' tate fabric are entered in the dyebath; the temperature is raised to 80 in minutes and this temperature maintained for 1 hour. Then the fabric is removed from the dyebath, rinsed with water and dried. A bright blue dyeing is obtained which has excellent light fastness and goodfa stness towashing, perspiration and gas fumes.

Example 3 100 puarts of ,Dacron polyethylene terephthalate fibers made by the condensation of dimethyl terephthalate and .ethylene glycol, (see Handbook of Material Trade Names, by Zimmermann and Lavoine, 1953 edition, p; 159) are entered in a dyebath at 60 containing 3000 parts of Water, 2 parts of the dyestuifused in Example 1, and 1.5 parts of 2-hydroxy-1.1-diphenyl. The dyebath is brought to the 'boil in 20 minutesand boiled for 1 hour. The goods are then removed, rinsed with, water and dried. The Dacron fabric is dyed an attractive blue shade which is fast to washing and has very good fastness to light, heat setting and pleating. Cotton present in the dyebath is reserved.

Example 4 A fine dyestufl dispersion is prepared with 1 part of 1.5-dihydroxy-4.8-diamino -.2 (4-ethoxy)-phenylanthraquinone, 1 part of sulfite cellulose waste liquor (in powder form) and 8 parts of water. This paste is added to a dyebath of 3000 par-ts of water and 3 parts of Igepon T in a high-temperature dyeing machine. '100 parts of Terylene polyester fiber are added, the machine closed, and the inner temperature increased to 120. After 1 hour at this temperature dyeing is completed. The material is removed, rinsed and dried. It is dyed a blue shade which shows good washing and perspiration fastness and very good fastness to light, heat setting and pleating. Wool present in the dyebath is reserved. Dacron, Dralon and Tergal polyester fibers can be dyed by the same method.

' Example 5 1 part. of. 1.5-dihydroxy-4.8-diamino-2-(4'methoxy)- phenylanthraquinone, 1 part of the sodium salt of dinaphthylme'thanedisulfonic acid and 8 parts of water are,

ground together until a fine dispersion is obtained. It is run into a dyebath containing '4000 parts of water and 4 parts of a highly sulfonated castor oil. 100 parts of a Nylon 66 fabric are entered in the bath and the temperature is increased to 100 in minutes. Dyeing is continued for 1 hour at 95-100? The nylon is then rinsed in warm and cold water and dried. I Itis dyed a bright blue shade which has; very good fastness to Washing and perspiration and good light. fastness.

' With other synthetic polyamide fibers such as Perlon (=Nylon 6), Mirlon, Grilon or Rilsan dyeings of similar fastness properties are obtained.

In thefollowing table, are listediu'rtherdyestulfs of Formula I which are highly suitable for dyeing cellulose acetate, cellulose tn'acetate, and synthetic polyamide polyesterv fibers. They are characterized in the table by the hydrocarbon radical RH forming the basis of the radical R, the dyeing material, and the shade of the dyeing.

Example Dyeing Ma- Shade of No. R-H terial the Dyeing 6 phenoxybenzene Dacron blue l-hydroxy-Z-chlorobenzene do regihsh ue. l-hydroxy-Z-methylbenzene acetate sky- 1-hydroxy-3-rnethylbenzene. l-hydroxy--methylbenzene l-hydroxy-i-ethylbenzene.

l-h ydroxynaph thalene 13 2-hydroxynaphthalene.

14 1-hydroxy-2-amylbenzene 15 1-hydroxy-4-arnylbenzene acetate.

16 l-hydroxyt-octylbenzene d 17 l-hydroxyl-cyelohexylbenzene 18 l-hydroxy-2-phenylbenzene 19 1-hydroxy-4-phenylbenzene 20 1 hydroxy 2.6 di isopropyl benzene. 1 hydroxy 2 tert.buty1 5 methylbenzene. 1hydroxy-2.6-dimethylbenzene Lzdimethoxybenzene lA-dimethoxybenzene. 1-hydroxy-2-n1ethoxybenzene. l-hydroxyi-methoxybenzene...

(2"-hydroxy)-ethoxybenzene cellulose-tri- Do. acetate. 7 L 1.2-dihydroxybenzene Dacron blue- L3-dihydroxybenzene 1.4-dihydroxybenzene l-methoxyi-methylbenzene.

4-amino-phen0xybenzene 1-methoxy-4-propenylbenzene. 1 hy droxy- 2 methoxy 4 allyl benzene.

[2-(2-hydroxy) -ethoxy]ethoxybenzene. 1.3.5-trihydroxybenzene 1 -hydroxy 2 benzoyl 5 methoxybenzene.

2.2 bis(4 hydroxyphenyl) propane.

2-bromethoxybenzene 2-chlorethoxybenzene 3'-methoxypropoxybenzene 2 -ethoxyethoxybenzene l-hydroxyl-ethoxybenzene Nylon 66.. acetate Example 44 boiled for 1 hour. The goods are then removed, rinsed with Water and dried. The Dacron fabric is dyed an attractive blue shade which is fastto washing and has very good fastness to light, heat setting and pleating. Cotton or wool present in the dyebath is reserved.

Other dyestuff mixtures suitable for the dyeing of acetate, triacetate and polyester fibers are e.g. the following: 1.5-dihydroxy-4.S-diamino 2 (4,-methoxy)-phenylan-, thnaquinone and 1.5dihydroxy 4.8 diainino-Z-(Z-hydroXy-S-amyl)rphenylanthraquinone, 1.5 dihydroxy-4-.8- diamino-YZ-( V-methoxy)-phenylanth raquinone and 1.5-dihydroxy 4.8 diamino-2-'(4'-ethoxy)-phenylanthraquinone, 1.5-dihydroxy-4.S-diamino-Z- (4'-ethoxy) -plienylanthraquinone and 1.5-dihydroxy 4.8 diamino-2-(4'-hydroxy)-phenylanthraquinone, etc. When used in equal concentration these mixtures yield stronger dyeings than the dyestuff 1.5dihydroxy 4.8 diamino-2(4-methoxy)- phenylanthraquinone alone. In the case of weak dyeings the exhaust (i.e. the patterns used in the second dyeing proce'ss) remain white,

Having thus disclosed the invention what I claim is:

l. A dyeing process comprising applying to an artificial fiber material selected from the group consisting of secondary cellulose acetate, cellulose triacetate, and polyethylene terephthalate fibers, from an aqueous dispersion,

a member selected from the group consisting of a single anthraquinone dyestufi and a mixture of anthraquinone dyestulfs of the formula OH O NHQ (OX) n Z NHz OH wherein R represents a member selected from the group consisting of radicals of the benzene, diphenyl and naphthalene series,

X represents a member selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl, lower hydroxy-alkoxyalkyl, lower halogeno-alkyl, phenyl and aminophenyl,

Y represents a member selected from the group consisting of hydrogen, alkyl with 1 to 8 carbon atoms, alkoxy with 1 to 2 carbon atoms, alkenyl with 3 carbon atoms, cyclohexyl and chlorine provided that the latter stands in an other than the para-position to the OX-group,

Z represents a member selected from the group consisting of hydrogen, lower alkyl and lower alkoxy,

n represents one of the integers l, 2 and 3.

and

2. A dyeing process comprising applying to an artificial fiber material selected from the group consisting of secondary cellulose acetate, cellulose triacetate, and polyethylene terephthalate fibers, from an aqueous dispersion, the anthraquinone dyestutf of the formula C 5114-0 C H; l NH: Cl H 3. A dyeing process comprising applying to an artificial fiber material selected from the group consisting of secondary cellulose acetate, cellulose triacetate, and poly- 4. A dyeing process comprising applying to an artificial fiber material selected -from the group consisting of second-ary cellulose acetate, cellulose triacetate, and polyethylene terep'hthalate fibers, from an aqueous dispersion, the anthraquinone dyestuff of the formula 5. A dyeing process comprising applying to an artificial fiber material selected from the group consisting of secondary cellulose acetate, cellulose triacetate, and polyethylene terephthalate fibers, from an aqueous dispersion, a mixture of the two dyestuffs of the formulae OH O NHz I l I CBH4OH II I NH2 0 OH and (i)H NHi mOIHAOOHE I ll NH2 0 OH 6. A dyeing process comprising applying to an artificial fiber material selected from the group consisting of secondary cellulose acetate, cellulose triacet-ate, and polyethylene terephthalate fibers, from an aqueous dispersion, the anthraquinone dyestufi of the formula NH; O OH References Cited in the file of this patent UNITED STATES PATENTS 2,922,691 Grossman 'Jan. 26, 1960 2,993,917 Weinstein et a1 July 25, 1961 FOREIGN PATENTS 456,235 Germany Feb. 18, 1928 OTHER REFERENCES Dorm-an: Amer. Dyest Rep., July 5, 1954, pages 426- 429, 437 (esp. p. 428).

Schroeder: Text, Res. 1., vol, 27, No. 4, April 1957, pp. 275-285. 36Ygates: Silk J. and Rayon World, November 1945, pp.

Patent No. 3,043 646 Paul Buecheler Column 5, line 27, before "n" and in italics, insert line 28, strike out "and" Signed and sealed this 16th day of June 1964.

SEAL) I ttest:

ERNEST W. SWIDER EDWARD J. BRENNER testing Officer Commissioner of Patents 

1. A DYEING PROCESS COMPRISING APPLYING TO AN ARTIFICIAL FIBER MATERIAL SELECTED FROM THE GROUP CONSISTING OF SECONDARY CELLULOSE ACETATE, CELLULOSE TRIACETATE, AND POLYETHYLENE TEREPHTHALATE FIBERS, FROM AN AQUEOUS DISPERSION, A MEMBER SELECTED FROM THE GROUP CONSISTING OF A SINGLE ANTHRAQUINONE DYESTUFF AND A MIXTURE OF ANTHRAQUINONE DYESTUFFS OF THE FORMULA 